CN115448379A - Preparation method and application of positive active material precursor - Google Patents
Preparation method and application of positive active material precursor Download PDFInfo
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- CN115448379A CN115448379A CN202211061432.4A CN202211061432A CN115448379A CN 115448379 A CN115448379 A CN 115448379A CN 202211061432 A CN202211061432 A CN 202211061432A CN 115448379 A CN115448379 A CN 115448379A
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- active material
- mixed salt
- gas
- precursor
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 140
- 239000002243 precursor Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 145
- 150000003839 salts Chemical class 0.000 claims abstract description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000008139 complexing agent Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000975 co-precipitation Methods 0.000 claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 claims 1
- XOJITQHBMRQMRX-UHFFFAOYSA-M sodium;ethane-1,2-diamine;2-oxido-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound [Na+].NCCN.[O-]P1(=O)OCCCCO1 XOJITQHBMRQMRX-UHFFFAOYSA-M 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000012716 precipitator Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000006182 cathode active material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 229910013952 LiNi0.3Co0.5Mn0.2O2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method and application of a precursor of a positive active material. The preparation method of the precursor of the positive electrode active material comprises the following steps: carrying out coprecipitation reaction on lithium hydroxide, a mixed salt system and a complexing agent to obtain a precursor of the positive active material; the mixed salt system comprises at least a nickel source; the mixed salt system further includes at least one of a cobalt source, an aluminum source, and a manganese source. According to the method, lithium hydroxide is used as a precipitator, a complexing agent is added in the process of coprecipitation reaction, a positive active material precursor can be prepared, the positive active material with excellent electrochemical performance can be prepared by using the positive active material precursor, other impurity ions are not introduced in the preparation method, the removal of the impurity ions does not need to be comprehensively considered, and the production cost is low.
Description
Technical Field
The invention relates to a preparation method and application of a precursor of a positive active material, belonging to the technical field of new energy.
Background
In recent years, batteries are being developed toward high energy density, long cycle life, and high safety performance. The positive active material is a key to determine the energy density of the battery.
In the prior art, sodium hydroxide is usually used as a precipitant, a nickel cobalt manganese hydroxide precursor is obtained by a coprecipitation method, and then the nickel cobalt manganese hydroxide precursor and a lithium source are calcined at a high temperature to synthesize the positive active material. In the method, however, on one hand, the nickel-cobalt-manganese hydroxide precursor generated by coprecipitation does not have a pore channel suitable for lithium ion deintercalation, so that a lithium source is difficult to be uniformly embedded into the nickel-cobalt-manganese hydroxide precursor in the high-temperature calcination process, and the electrochemical performance of the finally obtained positive active material is further influenced; on the other hand, because sodium hydroxide is used as a precipitating agent, not only the comprehensive consideration of Na is required + The impurity removal process increases the production cost, and Na + Is easily introduced into the finally formed cathode active material, thereby reducing the electrochemical performance of the later cathode active material.
Disclosure of Invention
The invention provides a preparation method of a positive active material precursor, which takes lithium hydroxide as a precipitator, and a complexing agent is added in the process of coprecipitation reaction, so that the positive active material precursor can be prepared.
The invention provides a positive active material precursor, which can be used for preparing a positive active material with excellent electrochemical performance and is low in preparation cost.
The invention provides a positive electrode active material which has excellent electrochemical performance and lower production cost.
The invention provides a preparation method of a precursor of a positive electrode active material, which comprises the following steps: carrying out coprecipitation reaction on lithium hydroxide, a mixed salt system and a complexing agent to obtain a precursor of the positive active material;
the mixed salt system comprises at least a nickel source;
the mixed salt system further includes at least one of a cobalt source, an aluminum source, and a manganese source.
The preparation method as described above, wherein the complexing agent is at least one selected from the group consisting of ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium chloride, glycine, diethanolamine, triethanolamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, sodium ethylenediamine tetramethylidene phosphate, diethylenetriamine pentamethylenephosphonate, aminotrimethylene phosphate, polyacrylic acid, sodium pyrophosphate, tartaric acid, citric acid, ammonium citrate, sodium citrate, oxalic acid, sodium oxalate, acetic acid, maleic acid, succinic acid, malonic acid, and crown ether.
The preparation method as described above, wherein, in the mixed salt system, the molar content x of the nickel element satisfies: x is more than 0.1 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content y of the manganese element satisfies that y is more than or equal to 0 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content z of the cobalt element meets the following requirements: z is more than or equal to 0 and less than 0.3; and/or the presence of a gas in the atmosphere,
in the mixed salt system, the molar content w of the aluminum element meets the following requirements: w is more than or equal to 0 and less than 0.3.
The preparation method as described above, wherein, in the lithium hydroxide solution, the molar concentration of lithium ions is 2-5mol/L; and/or the presence of a gas in the gas,
the flow rate of the lithium hydroxide solution is 3-5mL/min; and/or the presence of a gas in the gas,
the molar concentration of metal ions in the mixed salt system solution is 1-2.5mol/L.
The preparation method is characterized in that the flow rate of the mixed salt system solution is 5-7mL/min; and/or the presence of a gas in the gas,
the flow rate of the complexing agent solution is 0.1-5mL/min; and/or the presence of a gas in the gas,
the concentration of the complexing agent solution is 0.01-10mol/L.
The preparation method as described above, further comprising: mixing the complexing agent with the mixed salt system to obtain a mixed salt-complexing system;
and carrying out coprecipitation reaction on the mixed salt-complexing system and the lithium hydroxide to obtain the precursor of the positive active material.
The preparation method as described above, wherein, in the mixed salt-complexing system, the concentration of the complexing agent is 0.01-10mol/L; and/or the presence of a gas in the gas,
the flow rate of the mixed salt-complexing system is 5-7mL/min.
The preparation method as described above, further comprising: sequentially carrying out aging treatment and filtering treatment on a coprecipitation system obtained by the coprecipitation reaction to obtain a precipitation product;
and washing the precipitation product to obtain the precursor of the positive active material.
The invention provides a positive electrode active material precursor, which is prepared by the preparation method of the positive electrode active material precursor.
The present invention provides a positive electrode active material obtained by subjecting a system including the positive electrode active material precursor described above to a calcination treatment.
The invention provides a preparation method of a positive active material precursor, which is characterized in that lithium hydroxide is used as a precipitator to carry out coprecipitation reaction on a mixed salt system at least comprising a nickel source and a manganese source, and a complexing agent is added in the coprecipitation reaction to promote the coprecipitation reaction, so that the positive active material precursor can be prepared, can be used for preparing a positive active material with excellent electrochemical performance, and can not introduce other impurity ions (especially Na) in the preparation method + ) The removal of impurity ions does not need to be considered comprehensively, and the production cost is low.
The invention provides a positive active material precursor, which can be used for preparing a positive active material with excellent electrochemical performance and is low in preparation cost.
The invention provides a positive electrode active material which has excellent electrochemical performance and lower production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is an SEM image of a positive electrode active material precursor in example 1 of the present invention;
fig. 2 is an SEM image of the positive electrode active material in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first aspect of the present invention provides a method for preparing a precursor for a positive electrode active material, including: carrying out coprecipitation reaction on lithium hydroxide, a mixed salt system and a complexing agent to obtain a precursor of the positive active material;
the mixed salt system at least comprises a nickel source;
the mixed salt system further includes at least one of a cobalt source, an aluminum source, and a manganese source.
In the invention, lithium hydroxide, a mixed salt system and a complexing agent are subjected to coprecipitation reaction, and the obtained precipitation product is the precursor of the positive active material. In the coprecipitation reaction, lithium hydroxide, which acts as a precipitant, can be mixed with the mixed salt system to produce a precipitate. And a complexing agent is also added in the precipitation process, and can complex lithium ions, so that the concentration of the lithium ions is increased, the application range of the lithium ions as an alkaline precipitator is increased, and a precursor of the positive active material with excellent performance is formed.
It is understood that the mixed salt system of the present invention includes at least a nickel source and may further include at least one of a cobalt source, an aluminum source, and a manganese source. For example, the mixed salt system of the present invention may include a nickel source as well as a cobalt source; nickel, aluminum and manganese sources may also be included; nickel sources as well as manganese sources may also be included.
The temperature of the coprecipitation reaction is not particularly limited in the present invention, and in some embodiments, the temperature of the coprecipitation reaction is 45 to 70 ℃.
In some embodiments, during the coprecipitation reaction, stirring treatment may be performed at a rotation speed of 300 to 100r/min.
It can be understood that after the lithium hydroxide, the mixed salt system and the complexing agent are subjected to coprecipitation reaction, a coprecipitation system comprising a precipitation product is formed, the coprecipitation system is aged to precipitate more precipitation products, and then filtration treatment is performed to obtain the precipitation product.
In some embodiments, the aging treatment is carried out for a time of 0.2 to 12 hours at a temperature of 40 to 60 ℃.
The precipitated product may also be post-treated to obtain a pure precursor of the positive active material. The post-treatment comprises the following steps: and washing the precipitate to obtain a washed product, and drying the washed product to obtain a pure precursor of the positive active material. Specifically, the precipitated product may be subjected to a washing treatment using water, or may be subjected to a washing treatment using a lithium hydroxide solution. Further, the precipitate is washed with a lithium hydroxide solution and then with water, whereby a more pure precursor of the positive electrode active material can be obtained.
In some embodiments, the washing time is 20-60min, and the temperature is 40-60 ℃; the drying treatment can be forced air drying or vacuum drying, and the drying treatment temperature is 80-120 deg.C and the drying treatment time is 8-24h.
In the invention, the filtered filtrate and the washed washing liquid can be recycled to obtain the lithium hydroxide, and the obtained lithium hydroxide can be returned to participate in the coprecipitation reaction. And the residual nickel element and manganese element in the filtrate and the washing liquid can be recovered to participate in the coprecipitation reaction.
The nickel source is not particularly limited in the present invention, and a salt containing nickel element commonly used in the art may be selected, and for example, at least one of nickel sulfate, nickel chloride and nickel nitrate may be used. The manganese source is not particularly limited in the present invention, and a salt containing manganese element commonly used in the art may be selected, and for example, at least one of manganese sulfate, manganese chloride and manganese nitrate may be used. The cobalt source is not particularly limited in the present invention, and a salt containing cobalt element commonly used in the art may be selected, and for example, at least one of cobalt sulfate, cobalt chloride and cobalt nitrate may be used.
The complexing agent is not particularly limited in the present invention, and a complexing agent commonly used in the art may be selected. For example, the complexing agent may be ammonia.
According to the invention, lithium hydroxide is used as a precipitator to carry out coprecipitation reaction on a mixed salt system at least comprising a nickel source and a manganese source to prepare the precursor of the positive active material, on one hand, because the lithium hydroxide is added in the preparation process of the precursor of the positive active material, the lithium hydroxide can enable the precursor of the positive active material to have a pore channel suitable for lithium ion deintercalation, the lithium source can be uniformly inserted into the precursor of the positive active material in the high-temperature calcination process, and the electrochemical performance of the precursor of the positive active material is improved; on the other hand, sodium ions are not introduced in the preparation process of the precursor of the positive active material, so that the sodium ions are not introduced into the positive active material, the electrochemical performance of the positive active material is improved, and the impurity removal process of the sodium ions is not required to be considered after the coprecipitation reaction because the sodium ions are not introduced, so that the production cost is saved.
It is worth mentioning that the complexing agent is added in the coprecipitation reaction, and the addition of the complexing agent solves the problem of heterogeneous nucleation caused by different precipitation Ksp of different metal elements under the condition of no complexing agent; the addition of the complexing agent can also improve the saturation concentration of LiOH in the solution, increase the applicability of the LiOH as an alkaline precipitator, and contribute to forming a precursor of the cathode active material with excellent performance, thereby forming the cathode active material with excellent electrochemical performance.
In some embodiments of the invention, the complexing agent is selected from at least one of ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium chloride, glycine, diethanolamine, triethanolamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, sodium ethylenediamine tetra-methylphosphonate (EDTMPS), diethylenetriamine penta-methylenephosphonate (DETPMPS), aminotrimethylene phosphate, polyacrylic acid, sodium pyrophosphate, tartaric acid, citric acid, ammonium citrate, sodium citrate, oxalic acid, sodium oxalate, acetic acid, maleic acid, succinic acid, malonic acid, and crown ether.
According to the invention, the complexing agent can be used for forming the anode active material precursor with excellent performance so as to form the anode active material with excellent electrochemical performance, and the complexing agent except ammonia water can avoid a subsequent ammonia evaporation process, can also avoid generation and volatilization of irritant gas in the preparation process of the anode active material precursor, and can improve the working environment of a workshop.
Furthermore, the molar content of the nickel element, the molar content of the manganese element, the molar content of the cobalt element and the molar content of the manganese element in the mixed salt system can be specifically selected, so that the performance of the obtained precursor of the cathode active material is more excellent.
For example, in the mixed salt system, the molar content x of the nickel element satisfies: x is more than 0.1 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content y of the manganese element meets the following requirements: y is more than or equal to 0 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content z of the cobalt element meets the following conditions: z is more than or equal to 0 and less than 0.3; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content w of the aluminum element satisfies the following condition: w is more than or equal to 0 and less than 0.3.
The specific form of the coprecipitation reaction of the lithium hydroxide, the mixed salt system and the complexing agent is not particularly limited. For example, in some embodiments of the present invention, a lithium hydroxide solution, a mixed salt system solution, and a complexing agent solution may be prepared separately, and then the lithium hydroxide solution, the mixed salt system solution, and the complexing agent solution may be subjected to a coprecipitation reaction to obtain a positive active material precursor.
In some embodiments, the flow rate of the lithium hydroxide solution is 3 to 5ml/min, the flow rate of the mixed salt system solution is 5 to 7ml/min, and the flow rate of the complexing agent solution is 0.1 to 5ml/min; in the lithium hydroxide solution, the molar concentration of lithium ions is 2-5mol/L, in the mixed salt system solution, the molar concentration of metal ions is 1-2.5mol/L, and the concentration of the complexing agent solution is 0.01-10mol/L.
In some embodiments of the invention, further comprising: mixing a complexing agent with the mixed salt system to obtain a mixed salt-complexing system;
and carrying out coprecipitation reaction on the mixed salt-complexing system and the lithium hydroxide to obtain the precursor of the positive active material.
In the invention, a mixed salt system solution and a lithium hydroxide solution can be prepared respectively; then mixing the complexing agent and the mixed salt system solution to obtain a mixed salt-complexing system containing the complexing agent; and then carrying out coprecipitation reaction on the mixed salt-complexing system containing the complexing agent and the lithium hydroxide solution to obtain the precursor of the positive active material.
In some embodiments of the present invention, a certain amount of deionized water may be added to the reaction vessel as a base solution, the base solution is heated and stirred, and then lithium hydroxide is added to the base solution to adjust the pH of the base solution to 11.3-11.7. The operation can also promote the coprecipitation reaction and improve the performance of the precursor of the positive active material.
In some embodiments of the present invention, the concentration of the complexing agent in the mixed salt-complexing system, the concentration and flow rate of the lithium hydroxide solution, the concentration of the metal ions in the mixed salt system solution, and the flow rate of the mixed salt-system may be specifically selected to efficiently perform the coprecipitation reaction, thereby forming a precursor of the positive electrode active material having excellent properties.
For example, in the mixed salt-complexing system, the concentration of the complexing agent is 0.01 to 10mo/L.
In the lithium hydroxide solution, the molar concentration of lithium ions is 2-5mol/L; and/or the presence of a gas in the gas,
the flow rate of the lithium hydroxide solution is 3-5ml/min.
In the mixed salt system solution, the molar concentration of metal ions is 1-2.5mol/L; and/or the presence of a gas in the gas,
the flow rate of the mixed salt-complexing system is 5-7ml/min.
The second aspect of the invention provides a positive electrode active material precursor, which is prepared by the preparation method of the positive electrode active material precursor.
The precursor of the positive electrode active material can be used for preparing the positive electrode active material with excellent electrical property due to being prepared by the preparation method, and the preparation cost of the precursor of the positive electrode active material is low.
A third aspect of the invention provides a positive electrode active material obtained by subjecting a system including the positive electrode active material precursor described above to a calcination treatment.
In the present invention, the positive active material precursor may be prepared into the positive active material using a calcination process commonly used in the art.
In some embodiments, the positive electrode active material precursor of the present invention and the lithium source may be co-calcined. Wherein, the lithium source can be lithium hydroxide or lithium carbonate, and the molar ratio of the lithium source to the positive active material precursor is (1-1.5): 1.
in some embodiments, a calcination treatment can be used, the temperature is 500-800 ℃, the heating rate is 2-10 ℃/min, and the holding time is 6-24h.
In other embodiments, two-stage calcination treatment can be adopted, wherein the temperature of the first stage calcination treatment is 300-650 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 2-6h; the temperature of the second stage of calcination treatment is 600-850 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 6-12h.
The cathode active material of the invention is prepared by using the cathode active material precursor, so that the cathode active material has excellent electrochemical performance.
The technical solutions of the present invention are further illustrated below with reference to specific examples, all reagents used in the examples are commercially available or synthesized according to conventional methods, and can be used directly without further treatment, and the instruments used in the examples are commercially available.
Example 1
The positive electrode active material precursor and the positive electrode active material of the present embodiment are prepared by a method including the steps of:
1) Preparation of precursor of positive electrode active material
A. Adding a certain amount of deionized water into a reaction kettle, stirring and heating until the temperature is 55 ℃, introducing nitrogen into the reaction kettle, and adding lithium hydroxide to adjust the pH value of the deionized water to 11.5;
B. adding EDTA into the mixed salt system solution to obtain a mixed salt-complexing system solution; introducing a lithium hydroxide solution and a mixed salt-complexing system solution into a reaction kettle to carry out coprecipitation reaction, and stopping feeding when the D50 of a precipitated product is 10 micrometers to obtain a precipitation system;
the concentration of lithium ions in the lithium hydroxide solution is 5mol/L, the mixed salt system comprises a nickel source, a cobalt source and a manganese source, the nickel source, the cobalt source and the manganese source are all sulfates, the concentration of metal ions in the mixed salt system solution is 1.5mol/L, and the molar content of nickel elements in the mixed salt system is as follows: molar content of cobalt element: molar content of manganese element =8:1:1;
the concentration of EDTA in the mixed salt-complexing system solution is 0.01mol/L; the flow rate of the lithium hydroxide solution is 6.3mL/min, and the flow rate of the mixed salt-complexing system solution is 3.78mL/min;
C. aging the precipitation system, filtering to obtain a precipitation product, washing the precipitation product with deionized water, and drying the washed precipitation product to obtain a precursor of the positive electrode active material;
wherein the aging treatment temperature is 55 ℃, and the aging treatment time is 2h; the washing treatment time is 30min, and the temperature is 50 ℃; the drying temperature is 100 ℃ and the drying time is 12h.
2) Preparation of positive electrode active material
Calcining the lithium source and the precursor of the positive electrode active material obtained in the step 1) to obtain the LiNi positive electrode active material 0.8 Co 0.1 Mn 0.1 O 2 ；
Wherein the lithium source is LiOH, and the molar ratio of the lithium source to the precursor of the positive active material is 1.05:1, the temperature of the calcination treatment is 750 ℃, and the temperature is kept for 16h.
The morphology of the positive electrode active material precursor obtained in example 1 and the morphology of the positive electrode active material were observed by SEM, respectively.
Fig. 1 is an SEM image of a positive electrode active material precursor in example 1 of the present invention; fig. 2 is an SEM image of the positive electrode active material in example 1 of the present invention. As shown in fig. 1 and fig. 2, the surface of the precursor particle of the positive electrode active material has a complex structure, which indicates that the precursor particle of the positive electrode active material has high surface activity and specific surface area, is beneficial to lithiation reaction in a later sintering process, and is beneficial to improving rate capability and cycle performance of the positive electrode active material.
Example 2
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
1) Preparation of positive electrode active material
A. Adding a certain amount of deionized water into a reaction kettle, stirring and heating until the temperature is 55 ℃, introducing nitrogen into the reaction kettle, and adding lithium hydroxide to adjust the pH value of the deionized water to 11.5;
B. introducing a lithium hydroxide solution, a mixed salt system solution and ammonia water into a reaction kettle to carry out coprecipitation reaction, and stopping feeding when the D50 of a precipitated product is 10 mu m to obtain a precipitation system;
the concentration of lithium ions in the lithium hydroxide solution is 5mol/L, the mixed salt system comprises a nickel source, a cobalt source and a manganese source, the nickel source, the cobalt source and the manganese source are all sulfates, the concentration of metal ions in the mixed salt system solution is 1.5mol/L, and the molar content of nickel elements in the mixed salt system is as follows: molar content of cobalt element: molar content of manganese element =8:1:1, the concentration of ammonia water is 0.286mol/L;
the flow rate of the lithium hydroxide solution is 6.3mL/min, the flow rate of the mixed salt system solution is 3.78mL/min, and the flow rate of the ammonia water is 0.5mol/L;
C. aging the precipitation system, filtering to obtain a precipitation product, washing the precipitation product with deionized water, and drying the washed precipitation product to obtain a precursor of the positive electrode active material;
wherein the aging treatment temperature is 55 ℃, and the aging treatment time is 0.5h; the washing treatment time is 30min, and the temperature is 50 ℃; the drying temperature is 100 ℃ and the drying time is 12h.
2) Preparation of positive electrode active material
Calcining the lithium source and the precursor of the positive electrode active material obtained in the step 1) to obtain the LiNi positive electrode active material 0.8 Co 0.1 Mn 0.1 O 2 ；
Wherein the lithium source is LiOH, and the molar ratio of the lithium source to the precursor of the positive active material is 1.05:1, the temperature of the calcination treatment is 750 ℃, and the temperature is kept for 16h.
Example 3
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
glycine was used instead of EDTA, and the concentration of glycine in the mixed salt-complexing system solution was 0.06mol/L.
Example 4
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
triethanolamine was used in place of EDTA, and the concentration of triethanolamine in the mixed salt-complex system solution was 0.02mol/L.
Example 5
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
sodium pyrophosphate was used in place of EDTA and the concentration of sodium pyrophosphate in the mixed salt-complexing system solution was 0.02mol/L.
Example 6
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
aminotrimethylene phosphate was used in place of EDTA and the concentration of aminotrimethylene phosphate in the mixed salt-complexing system solution was 0.01mol/L.
Example 7
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
tartaric acid was used instead of EDTA and the concentration of tartaric acid in the mixed salt-complex system solution was 0.01mol/L.
Example 8
The positive electrode active material precursor and the positive electrode active material preparation method of the present example are substantially the same as those of example 1, except that:
EDTA was replaced with ammonium sulfate, and the concentration of ammonium sulfate in the mixed salt-complexing system solution was 0.02mol/L.
Example 9
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
in the step 1), the molar content of nickel element in the mixed salt system is as follows: molar content of cobalt element: molar content of manganese element =6:2:2;
the aqueous ammonia was replaced with a polyacrylic acid solution, and the concentration of the polyacrylic acid solution was 0.06mol/L.
In the step 2), liNi which is a positive electrode active material is obtained 0.6 Co 0.2 Mn 0.2 O 2 ；
The temperature of the calcination treatment is 850 ℃, and the temperature is kept for 20h.
Example 10
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
in the step 1), the mixed salt system comprises a nickel source, a cobalt source, a manganese source and an aluminum source, wherein in the mixed salt system, the molar content of a nickel element is as follows: molar content of cobalt element: molar content of manganese element: the molar content of the aluminum element = 8;
the flow rate of the ammonia water is 0.6mol/L;
the aging time is 1h.
Obtaining a positive electrode active material LiNi in the step 2) 0.8 Co 0.1 Mn 0.05 Al 0.05 O 2 ；
The molar ratio of the lithium source to the positive electrode active material precursor is 1.03:1, the temperature of the calcination treatment is 800 ℃, and the temperature is kept for 16h.
Example 11
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
in the step 1), the molar content of nickel element in the mixed salt system is as follows: molar content of cobalt element: the molar content of manganese element = 1;
the flow rate of the aqueous ammonia was 0.6mol/L.
In the step 2), the positive active material Li is obtained 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 ；
The molar ratio of the lithium source to the positive electrode active material precursor was 1.5:1, the temperature of the calcination treatment is 800 ℃, and the temperature is kept for 16h.
Example 12
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
in the step 1), the mixed salt system comprises a nickel source and a manganese source, wherein the molar content of the nickel element in the mixed salt system is as follows: the molar content of the manganese element =3:1;
obtaining a positive electrode active material LiNi in the step 2) 0.75 Mn 0.25 O 2 ；
The parameters of the calcination treatment were: heating to 600 deg.C at a rate of 2 deg.C/min, maintaining for 5 hr, heating to 870 deg.C at a rate of 2 deg.C/min, maintaining for 9 hr, and cooling.
Example 13
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
in the step 1), the molar content of nickel element in the mixed salt system is as follows: molar content of cobalt element: molar content of manganese element =3
The final material is LiNi 0.3 Co 0.5 Mn 0.2 O 2 。
Example 14
The positive electrode active material precursor and the method for preparing the positive electrode active material in this example are substantially the same as those in example 2, except that:
the concentration of the complexing agent ammonia water is 0.005mol/L.
Comparative example 1
The positive electrode active material precursor and the positive electrode active material of this comparative example were prepared in substantially the same manner as in example 1, except that; EDTA was not used.
Comparative example 2
The positive electrode active material precursor and the positive electrode active material of this comparative example were prepared substantially in the same manner as in example 9, except that:
replacing the lithium hydroxide in step B with sodium hydroxide.
Test examples
Lithium ion batteries were respectively prepared using the positive active materials in examples and comparative examples, and the preparation of the lithium ion batteries included the following steps:
1) Preparation of positive plate
Coating the positive active slurry on two surfaces of an aluminum foil, then placing the aluminum foil coated with the positive active slurry in a 120 ℃ drying oven for drying for 2h, cutting the aluminum foil into a circular positive plate with the diameter of 10mm by using a punching machine, recording the quality of the circular positive plate, then placing the circular positive plate in a 120 ℃ vacuum drying oven for drying for 12h to remove moisture, and finally placing the circular positive plate in a glove box under the argon atmosphere for storage;
the positive active slurry comprises a positive material, acetylene black (a conductive agent) and polyvinylidene (a binder), and the mass ratio of the positive active material to the conductive agent to the binder is 96.5%:1.5%:2 percent; the surface loading capacity of the positive plate is 15mg/cm 2 。
2) Preparation of lithium ion battery
Assembling a lithium negative electrode shell, an elastic sheet, a gasket, a lithium metal negative electrode sheet, a diaphragm, the positive electrode sheet obtained in the step 1) and the positive electrode shell to form an electrode assembly, and injecting 30 microliters of electrolyte into the shell to obtain a lithium ion battery;
wherein the electrolyte comprises LiPF 6 EC, DEC and EMC, wherein the volume ratio of EC, DEC and EMC is 1:1:1,LiPF 6 The concentration of (2) is 1mol/L.
Performance test
The batteries obtained in the test examples were subjected to performance tests, the test results are shown in table 1,
the specific test parameters are as follows: the voltage window of battery charging and discharging is 3-4.3V, the capacity test is carried out according to 0.2C charging/0.2C discharging, the first effect test is carried out according to 0.5C charging/5C discharging, and the cycle stability test is carried out according to 0.2C charging/0.2C discharging for 100 weeks.
TABLE 1
As can be seen from table 1:
1) From examples 1-11 and 13-14 and comparative examples 1-2, it can be seen that the positive active material precursor prepared by using LiOH, a mixed salt system and a complexing agent can be sintered to obtain a positive active material, which can be used for preparing a battery with excellent discharge capacity, first effect and cycle capacity retention rate;
2) It can be seen from example 2 and examples 1 and 3 to 8 that the positive electrode active material precursor (examples 1 and 3 to 8) prepared by using the non-aqueous ammonia complexing agent and the positive electrode active material precursor (example 2) prepared by using the aqueous ammonia as the complexing agent have similar electrochemical properties, which indicates that the non-aqueous ammonia complexing agent is further selected to participate in the coprecipitation reaction, so that a subsequent ammonia evaporation process can be avoided on the premise of maintaining the electrochemical properties of the positive electrode active material precursor, and the generation and volatilization of an irritant gas can also be avoided in the preparation process of the positive electrode active material precursor, so that the working environment of a workshop can be improved;
3) From example 2 and example 13, it can be seen that the molar content x of the nickel element in the mixed salt system satisfies: x is more than 0.1 and less than 1, and the molar content y of the manganese element meets the following requirements: y is more than or equal to 0 and less than 1, and the molar content z of the cobalt element meets the following conditions: z is 0. Ltoreq. Z < 0.3 (example 2) compared with the positive electrode active material obtained without satisfying the above conditions (example 13), the electrochemical performance of the positive electrode material precursor obtained with satisfying the above conditions is excellent, and it is demonstrated that the electrochemical performance of the positive electrode active material precursor can be further improved by specifically selecting the content of the metal element in the mixed salt system according to the present invention.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on differences from other embodiments. The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing a precursor of a positive electrode active material, comprising: carrying out coprecipitation reaction on lithium hydroxide, a mixed salt system and a complexing agent to obtain a precursor of the positive active material;
the mixed salt system comprises at least a nickel source;
the mixed salt system further includes at least one of a cobalt source, an aluminum source, and a manganese source.
2. The method of claim 1, wherein the complexing agent is selected from at least one of ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium chloride, glycine, diethanolamine, triethanolamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, sodium ethylenediamine tetramethylene phosphate, diethylenetriamine pentamethylene phosphonate, aminotrimethylene phosphate, polyacrylic acid, sodium pyrophosphate, tartaric acid, citric acid, ammonium citrate, sodium citrate, oxalic acid, sodium oxalate, acetic acid, maleic acid, succinic acid, malonic acid, and crown ether.
3. The preparation method according to claim 1 or 2, characterized in that the molar content x of the nickel element in the mixed salt system satisfies: x is more than 0.1 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content y of the manganese element meets the following requirements: y is more than or equal to 0 and less than 1; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content z of the cobalt element meets the following conditions: z is more than or equal to 0 and less than 0.3; and/or the presence of a gas in the gas,
in the mixed salt system, the molar content w of the aluminum element meets the following requirements: w is more than or equal to 0 and less than 0.3.
4. The production method according to any one of claims 1 to 3, wherein the molar concentration of lithium ions in the lithium hydroxide solution is 2 to 5mol/L; and/or the presence of a gas in the gas,
the flow rate of the lithium hydroxide solution is 3-5mL/min; and/or the presence of a gas in the gas,
the molar concentration of the metal ions in the mixed salt system solution is 1-2.5mol/L.
5. The method according to any one of claims 1 to 4, wherein the flow rate of the mixed salt system solution is 5 to 7mL/min; and/or the presence of a gas in the gas,
the flow rate of the complexing agent solution is 0.1-5mL/min; and/or the presence of a gas in the gas,
the concentration of the complexing agent solution is 0.01-10mol/L.
6. The production method according to any one of claims 1 to 4, further comprising: mixing the complexing agent with the mixed salt system to obtain a mixed salt-complexing system;
and carrying out coprecipitation reaction on the mixed salt-complexing system and the lithium hydroxide to obtain the precursor of the positive active material.
7. The preparation method according to claim 6, wherein the concentration of the complexing agent in the mixed salt-complexing system is 0.01 to 10mo/L; and/or the presence of a gas in the gas,
the flow rate of the mixed salt-complexing system is 5-7mL/min.
8. The production method according to any one of claims 1 to 7, further comprising: sequentially carrying out aging treatment and filtering treatment on a coprecipitation system obtained by the coprecipitation reaction to obtain a precipitation product;
and washing the precipitation product to obtain the precursor of the positive active material.
9. A positive electrode active material precursor, characterized by being produced by the method for producing a positive electrode active material precursor according to any one of claims 1 to 8.
10. A positive electrode active material obtained by subjecting a system including the positive electrode active material precursor according to claim 9 to a calcination treatment.
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